CN104091932B - WS2nanometer sheet/graphene composite nano material with holes and preparation method - Google Patents
WS2nanometer sheet/graphene composite nano material with holes and preparation method Download PDFInfo
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- CN104091932B CN104091932B CN201410339886.2A CN201410339886A CN104091932B CN 104091932 B CN104091932 B CN 104091932B CN 201410339886 A CN201410339886 A CN 201410339886A CN 104091932 B CN104091932 B CN 104091932B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 8
- 239000002356 single layer Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 230000005611 electricity Effects 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention discloses a kind of WS2Nanometer sheet/graphene composite nano material with holes and preparation method thereof, it is by WS2Nanometer sheet with holes is compound with Graphene to be constituted, WS2Nanometer sheet with holes is monolayer or few number of plies, WS2And the ratio of the amount of the material between Graphene is 1:1 1:3.Its preparation method is first by graphene oxide ultrasonic disperse in deionized water, add cationic post [5] arene-based supermolecule, and be sufficiently stirred for, then it is sequentially added into L cysteine and sulfur for ammonium tungstate, is sufficiently stirred for making it dissolve, above-mentioned mixed dispersion is transferred in hydrothermal reaction kettle, at 230 250 DEG C after hydro-thermal reaction 20 24 h, naturally cool to room temperature, centrifugal collect solid product, wash, be dried, heat treatment acquisition.The method of the present invention has feature simply and easily, it is not necessary to consume organic solvent.
Description
Technical field
The present invention relates to composite nano materials and preparation method thereof, particularly relate to WS2Nanometer sheet/Graphene with holes is compound to be received
Rice material and hydrothermal preparing process thereof, belong to inorganic composite nano field of material technology.
Background technology
Two-dimensional ultrathin nanometer sheet material has the characteristic of numerous excellence with the pattern of its uniqueness, and its research causes people's
Great interest.Graphene is most typical two-dimensional nano sheet material, and the two-dimensional nano chip architecture of its uniqueness makes its numerous uniquenesses
The performances such as physics, chemistry and mechanics, have important scientific research meaning and technology application prospect widely.Graphene has pole
High specific surface area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, the characteristic of these excellences
Make Graphene before the aspects such as micro-nano electronic device, energy storage material and novel catalyst carrier have a wide range of applications
Scape.
The immense success that the discovery of Graphene and research thereof obtain excites people to other inorganic two-dimensional nano sheet material
The great interest of research, such as monolayer or the transition metal dichalcogenide etc. of few number of plies.As a kind of typical case and important transition gold
Belong to disulphide, WS2Have with graphite-like as layer structure, be the S-W-S unit that combines of covalent bond in its layer, layer and layer it
Between combination be more weak Van der Waals force.This typical layered structure and weak Van der Waals force, make WS2Have as kollag
There is relatively low friction factor, particularly still there is under the conditions of high temperature, fine vacuum etc. relatively low coefficient of friction, be a kind of excellent
Kollag.It addition, layer structure WS2The embedding of external atom or ion, therefore WS can be allowed2Lamellar compound is also
It is a kind of rising electrochemical lithium storage and storage Development of Magnesium Electrode Materials.
Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for
The inorganic material of layer structure, when its number of plies reduces (less than about 6 layers), especially reduce 4 layers and following time, its electronics
Character or band structure can produce significantly change, thus cause which show the physics different from corresponding body phase material and chemistry
Characteristic.In addition to Graphene, recent research indicate that when body phase WS2It is reduced to few number of plies (particularly during monolayer), it is shown that with body
The visibly different physics of phase material, chemistry and electronics property.Studies have reported that monolayer or the WS of few number of plies2There is more preferable electricity
Chemistry storage lithium performance and high electrocatalytic hydrogen evolution reactivity.But storage lithium electrode material and the electro-catalysis as electrochemical reaction
Material, WS2The lowest electric conductivity have impact on its application performance.
Due to WS2Nanometer sheet has similar two-dimensional nano sheet pattern with Graphene, and both tie at microscopic appearance and crystal
There is on structure good similarity.If by WS2Nanometer sheet and Graphene are combined the composite of preparation, graphene nano
The high conduction performance of sheet can improve the electric conductivity of composite further, strengthens electrochemistry storage lithium and electrocatalytic reaction process
In electron transmission, the electrochemistry storage lithium performance and electrocatalysis characteristic of composite can be improved further.WS2The electricity of nanometer sheet
The catalysis activity of catalytic hydrogen evolution reaction is mainly derived from its active sites edge, increases WS2The edge of nanometer sheet is that the electricity strengthened is urged
Change an approach of performance.WS as electrochemistry storage lithium electrode material, more multiple edge2Nanometer sheet can provide more and phase
To shorter lithium ion diffusion admittance, contribute to booster electrochemistry storage lithium performance.With common WS2Nanometer sheet compares, with holes
Nanometer sheet WS2There is more edge, with electrolyte, there is more contact area, its chemical property can be strengthened.Cause
This, this WS2The composite nano materials of nanometer sheet/Graphene with holes is urged as electrochemistry storage lithium electrode material and evolving hydrogen reaction electricity
The chemical property that agent has a wide range of applications and strengthens.
But, up to the present, WS2Nanometer sheet/graphene composite nano material with holes and preparation thereof have not been reported.This
Invent with graphene oxide and sulfur for ammonium tungstate as raw material, the hydrothermal method assisted by cationic post [5] arene-based supermolecule
Heat treatment subsequently, is prepared for WS2The composite nano materials of nanometer sheet/Graphene with holes.This preparation WS2Nanometer sheet with holes/
The method of the composite nano materials of Graphene has simple, convenient and is easily enlarged industrial applications a little.
Summary of the invention
It is an object of the invention to provide a kind of WS2Nanometer sheet/graphene composite nano material with holes and preparation method thereof,
This composite nano materials is by WS2Nanometer sheet with holes is compound with Graphene to be constituted, described WS2Nanometer sheet with holes is monolayer or few layer
The layer structure of number, described WS2The ratio of the amount of the material between nanometer sheet with holes and Graphene is 1:1-1:3.
The layer structure of few number of plies refers to that the number of plies is 6 layers or the layer structure of less than 6 layers.
WS of the present invention2The step of the preparation method of nanometer sheet/graphene composite nano material with holes is as follows:
(1) cationic post [5] arene-based supermolecule by graphene oxide ultrasonic disperse in deionized water, it is subsequently adding
(its structure is shown in Fig. 1), and be sufficiently stirred for；
(2) Cys and sulfur are sequentially added in the mixed system of step (1) for ammonium tungstate, and are stirred continuously and make L-
Cysteine and sulfur are completely dissolved for ammonium tungstate, and Cys and sulfur are 5:1 for the ratio of the amount of the material of ammonium tungstate consumption, sulfur
For the ratio of ammonium tungstate and the amount of the material of graphene oxide at 1:1-1:3；
(3) mixed dispersion that step (2) obtains is transferred in hydrothermal reaction kettle, and add deionized water adjustment body
Amassing 80% to hydrothermal reaction kettle nominal volume, the molar concentration of cationic post [5] arene-based supermolecule is 0.001 ~ 0.002
Mol/L, the molar concentration of graphene oxide is 30-65 mmol/L, puts in constant temperature oven by this reactor, 230-250 DEG C
After lower hydro-thermal reaction 20-24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fill with deionized water
Divide washing, be vacuum dried at 100 DEG C；By the solid product obtained by above-mentioned in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C
Lower heat treatment 2 h, in mixed gas, the volume fraction of hydrogen is 10%, prepares WS2Being combined of nanometer sheet/Graphene with holes
Nano material.
Above-mentioned graphene oxide uses the Hummers method improved to prepare.
The WS of the present invention2Nanometer sheet/graphene composite nano material with holes and preparation method thereof has the advantage that
Surface of graphene oxide and edge are with a lot of oxygen-containing functional groups (such as hydroxyl, carbonyl, carboxyl), these oxygen-containing senses
Group makes graphene oxide more easily be dispersed in water or organic liquid, but these oxygen-containing functional groups make surface of graphene oxide
With negative charge so that graphene oxide and the WS with negative charge4 2-Ion is incompatible, and the present invention passes through electrostatic interaction first will
Cationic post [5] arene-based supermolecule (its structure is shown in Fig. 1) is adsorbed onto surface of graphene oxide, WS4 2-Ion be just easier to
The graphene oxide interaction having adsorbed Gemini surface active agent combines.The more important thing is, with general quaternary ammonium salt
Cationic surfactant is compared, and the two ends of cationic post [5] arene-based supermolecule that the present invention uses are respectively arranged with the season of 5 positively chargeds
There is between ammonium hydrophilic group, and electronegative graphene oxide higher mutual electrostatic interaction；This cationic post [5] aromatic hydrocarbons
Supermolecule vertically or to adsorb in surface of graphene oxide in the way of lying low, and can be carried secretly in hydrothermal treatment process together
In hydrothermal product, in heat treatment process, cationic post [5] arene-based supermolecule is carbonized, and finally can prepare band
There is the most microporous WS2Nanometer sheet and the composite nano materials of Graphene.This WS2Nanometer sheet with holes not only has more work
Property edge, position, can strengthen its electrocatalysis characteristic to evolving hydrogen reaction, and the shortest lithium ion diffusion can be provided logical
Road, has assistant to strengthen its electrochemistry storage lithium performance.WS2Nanometer sheet/graphene composite material with holes can increase itself and electrolyte
Contact area, further help in and improve its chemical property.The preparation method of the present invention has simple, convenient and is prone to expand
The feature of big industrial applications.
Accompanying drawing explanation
Fig. 1 cationic post [5] arene-based supermolecule structural representation.
The WS that Fig. 2 embodiment 1 prepares2The XRD figure of nanometer sheet/graphene composite nano material with holes.
The WS that Fig. 3 embodiment 1 prepares2SEM shape appearance figure (a) of nanometer sheet/graphene composite nano material with holes and
Transmission electron microscope photo (b).
WS prepared by Fig. 4 comparative example2SEM shape appearance figure (a) of nanometer sheet/graphene composite nano material, TEM photo (b)
With HRTEM photo (c).
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Graphene oxide in following example uses the Hummers method improved to prepare: 0oUnder C ice bath, by 10.0
Mmol (0.12 g) graphite powder dispersed with stirring, in 50 mL concentrated sulphuric acids, is stirred continuously down and is slowly added into KMnO4, added KMnO4's
Quality is 4 times of graphite powder, stirs 50 minutes, when temperature rises to 35 DEG C, is slowly added into 50 mL deionized waters, is stirred for
30 minutes, add the H of 15 mL mass fractions 30%2O2, stir 30 minutes, through centrifugation, successively with mass fraction 5%
HCl solution, deionized water and acetone cyclic washing after obtain graphene oxide.
Embodiment 1.
1) by 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, add 0.16 mmol sun from
Subtype post [5] arene-based supermolecule, and be sufficiently stirred for；
2) 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfur then it are sequentially added into for ammonium tungstate, not
Disconnected stirring makes Cys and sulfur be completely dissolved for ammonium tungstate, with deionized water adjustment volume to about 80 mL；
3) transfer to obtained mixed liquor, in the hydrothermal reaction kettle of 100 mL, this reactor be put into constant temperature oven
In, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and use deionization
Water fully washs, at 100 DEG C be vacuum dried, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere 800
Heat treatment 2h at DEG C, prepares WS2The composite nano materials of nanometer sheet/Graphene with holes, the volume of hydrogen in mixed gas
Mark is 10%.
WS is obtained to prepared with XRD, SEM and TEM2The composite nano materials of nanometer sheet/Graphene with holes characterizes.
XRD analysis result shows WS in composite nano materials2The average number of plies be 2 layers of (see figure 2), SEM pattern and transmission electron microscope photo
(see Fig. 3) clearly demonstrates WS in composite the most respectively2Being the nanometer sheet of band micropore, its number of plies is at 1-3 layer, WS2With holes receive
WS in rice sheet/graphene composite nano material2It is 1:2 with the ratio of the amount of Graphene material.
Comparative example
Use Dodecyl trimethyl ammonium chloride cationic surfactant, be prepared for WS by above-mentioned similar approach2Nanometer
Sheet and the composite nano materials of Graphene, concrete preparation process is as follows:
By 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, add 1.6 mmol dodecyls
Trimethylammonium bromide cationic surfactant, and be sufficiently stirred for, then it is sequentially added into 0.76 g (6.25 mmol) L-half Guang
Propylhomoserin and 1.25 mmol sulfur are for ammonium tungstate, and are stirred continuously and make Cys and sulfur be completely dissolved for ammonium tungstate, spend from
Obtained mixed liquor, to about 80 mL, is transferred in the hydrothermal reaction kettle of 100 mL, by this reactor by sub-water adjustment volume
Put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid with centrifugation and produce
Thing, and fully wash with deionized water, it is vacuum dried at 100 DEG C, by obtained solid product at nitrogen/hydrogen mixed gas
In atmosphere at 800 DEG C heat treatment 2 h, in mixed gas, the volume fraction of hydrogen is 10%, prepares WS2Nanometer sheet/graphite
The nano composite material of alkene.
With XRD, SEM and TEM to finally preparing WS2Nanometer sheet characterizes with the nano composite material of Graphene,
XRD analysis result shows WS in composite nano materials2For layer structure, the average number of plies is 7 layers.SEM shape appearance figure, TEM photo and
HRTEM photo (see Fig. 4) shows the WS being supported on Graphene2For the pattern of nanometer sheet the most with holes, the main number of plies is 7 layers
Electrocatalytic reaction Hydrogen Evolution Performance test and comparison: by the WS of the 4 above-mentioned preparations of .0 mg2Nanometer sheet/Graphene with holes is multiple
Conjunction nano material (or WS prepared by comparative example2Nanometer sheet/graphene composite nano material) 1.0 mL deionization water-ethanol mix
Close in liquid (volume ratio 1:1), add the Nafion solution (5 wt%) of 30 uL, supersound process 2 h so that it is be sufficiently mixed
Being uniformly dispersed, obtain uniform slurry, the mixed slurry taking 5 uL with liquid-transfering gun drips on the glassy carbon electrode of diameter 5 mm,
Test job electrode is obtained after drying at 80 DEG C.Electrolyte is the aqueous sulfuric acid of 0.5 M, and reference electrode is saturated calomel electricity
Pole, platinized platinum, as to electrode, tests the material electricity to evolving hydrogen reaction with linear sweep voltametry on CHI660B electrochemical workstation
Catalytic performance is tested, and scanning speed is 5 mV/s.Test result shows under identical cathodic polarization overpotential, WS2Band
Hole nanometer sheet/graphene composite nano material electrode compares WS2Nanometer sheet/graphene composite nano material electrode has higher analysis
Hydrogen kinetic current, such as: under 0.20 V vs. RHE current potential, at WS2On nanometer sheet with holes/graphene composite nano material electrode
Electrochemical catalysis evolving hydrogen reaction electric current position 16.5 mA, at WS2Evolving hydrogen reaction on nanometer sheet/graphene composite nano material electrode
Electric current is 6.5 mA.Enhancing to evolving hydrogen reaction electrocatalysis characteristic is due to WS2Nanometer sheet/graphene composite nano material with holes
Middle WS2Nanometer sheet with holes compares WS2WS in nanometer sheet/graphene composite nano material2Nanometer sheet has more active sites edge.
It addition, WS2Nanometer sheet/graphene composite nano material with holes compares WS2Nanometer sheet/graphene composite nano material has more
Area with electrolyte contacts.
Claims (1)
1. a WS2The composite nano materials of nanometer sheet/Graphene with holes, it is characterised in that this composite nano materials is by WS2
Nanometer sheet with holes is compound with Graphene to be constituted, described WS2Nanometer sheet with holes be the number of plies be few number of plies of less than 6 layers stratiform knot
Structure, described WS2The ratio of the amount of the material between nanometer sheet with holes and Graphene is 1:1-1:3, the system of described composite nano materials
Preparation Method sequentially includes the following steps:
(1) by graphene oxide ultrasonic disperse in deionized water, it is subsequently adding cationic post [5] arene-based supermolecule, and fills
Divide stirring；
(2) then Cys and sulfur are added sequentially in the mixed system that step (1) obtains for ammonium tungstate, and constantly stir
Mixing and make Cys and sulfur be completely dissolved for ammonium tungstate, Cys and sulfur for the ratio of the amount of the material of ammonium tungstate consumption are
5:1, sulfur is 1:1-1:3 for the ratio of ammonium tungstate with the amount of the material of graphene oxide；
(3) mixed dispersion that step (2) obtains is transferred in hydrothermal reaction kettle, and add deionized water adjustment volume extremely
The 80% of hydrothermal reaction kettle nominal volume, cationic post [5] arene-based supermolecule molar concentration is 0.001～0.002mol/L,
The molar concentration of graphene oxide is 30-65mmol/L, puts in constant temperature oven by this reactor, hydro-thermal at 230-250 DEG C
After reaction 20-24h, allow it naturally cool to room temperature, collect hydro-thermal reaction solid product with centrifugation, and fill with deionized water
Point washing, is vacuum dried at 100 DEG C, by the hydro-thermal reaction solid product that obtains in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C
Lower heat treatment 2h, in mixed gas, the volume fraction of hydrogen is 10%, finally prepares WS2Nanometer sheet/Graphene with holes
Composite nano materials, the structural formula of described cationic post [5] aromatic hydrocarbons is as follows:
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